CN110305368A - 一种阻燃发泡剂及其制备方法和应用 - Google Patents
一种阻燃发泡剂及其制备方法和应用 Download PDFInfo
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Abstract
本发明公开了一种阻燃发泡剂及其制备方法，该制备方法将二维纳米材料和多元醇混合均匀后在80～120℃反应2～4h，然后加入增溶助剂和羟基硅胶混合均匀得到阻燃发泡剂。按原料总质量为100％计，阻燃发泡剂的原料组成包括：二维纳米材料0.1％～1％，多元醇30％～60％，增溶助剂0.1％～1％，羟基硅胶30％～70％。本发明还公开了一种阻燃硅橡胶泡沫材料，使用所述阻燃发泡剂作为发泡助剂，按原料总质量为100％计，原料组成包括：含氢硅油5％～25％，羟基硅胶10％～65％，发泡助剂0.1％～10％，抑制剂0.001％～4％，乙烯基硅油5％～50％，催化剂0.1％～3％。本发明绿色环保，制备工艺简单，制得的阻燃硅橡胶泡沫材料在航空航天、轨道交通、汽车、电子电器等领域有良好的应用前景。
Description
技术领域
本发明涉及有机硅泡沫材料领域，具体涉及一种阻燃发泡剂及其制备方法和应用。
背景技术
近年来随着航空领域的高速迅猛发展以及飞机、建筑等火灾事故的频繁发生，亟需发展一种既力学性能良好又同时兼备耐高低温和阻燃性能的多功能材料。泡沫材料(如聚氨酯、聚苯乙烯泡沫、密胺泡沫等)具有质轻、弹性好、价格低廉等优点，是较为理想的填充材料，但有一定的缺点和局限性，如耐高低温性能差、易燃烧且燃烧后产生有毒物质危害人体健康等。
硅橡胶材料是由“Si-O-Si”结构为主要骨架构成，由于硅氧元素之间键能较大，导致硅橡胶材料结构更稳定，不易被破坏；硅橡胶泡沫材料具有泡沫材料的共同优点，且兼具耐高低温性能和抗老化性能。相较于传统泡沫材料，有机硅橡胶泡沫材料具有广阔的应用前景。然而，由于硅橡胶分子侧基存在大量有机基团，如羟基、乙烯基、甲基、苯基等，其在高温下极易热降解，甚至会被点燃燃烧。为了改善硅橡胶泡沫材料的阻燃性能，目前主要有以下几个策略：
1、在硅橡胶基体中物理共混添加无机或有机阻燃剂：公开号为CN 106589956 A的专利说明书公开了一种低密度阻燃硅橡胶泡沫材料及其制备方法，在硅橡胶泡沫基体中加入10-50份的氢氧化铝和10-50份的聚磷酸铵有机阻燃填料，阻燃效果虽好，但高含量填充会造成密度增加、强度变差，不利于轻质和高强的需求。而纳米填料填充会大幅增加体系粘度，加工难度增大，难以获得卓越的阻燃效果。
2、利用化学的方法实现材料的本征阻燃：公开号为CN 107141806 A的专利说明书公开了一种本征阻燃硅橡胶泡沫材料的制备方法，该方法通过对硅油进行溴化改性，利用化学的方法实现材料的本征阻燃，此发明虽可有效提高硅橡胶泡沫材料的阻燃效果，但卤素的存在对环境存在一种潜在的危害，燃烧后会释放一种有毒物质危害人体健康和环境安全。
3、利用逐层自组装工艺(Layer by Layer)在材料表面涂敷一层或多层阻燃涂层：王玉忠等人通过逐层自组装技术在硅橡胶泡沫上组装制造了多层壳聚糖/聚磷酸铵和壳聚糖/蒙脱土纳米涂层，制备了阻燃的硅橡胶泡沫材料(DOI：10.1021/acs.iecr.6b00532)，但制备工艺过程较为复杂，难以尺度化，同时涂敷含量仍较高，另外存在多层涂层间及其与基材间界面作用可靠性差等缺点。
4、利用硅烷改性阻燃剂的方法制备阻燃硅橡胶泡沫材料：公开号为CN 108003619A的专利说明书公开了一种低含量石墨烯改性有机硅阻燃泡沫复合材料及其制备方法，该方法利用硅烷改性阻燃剂的方法来制备阻燃硅橡胶泡沫材料，但改性填料添加量为1wt％时才能实现硅橡胶泡沫的绿色高效阻燃，达到UL-94V0级。
从上述现有技术可知，现有的硅橡胶泡沫材料大多添加大量无机或有机阻燃剂，破坏了泡孔结构，影响材料回弹性及密度，或使用卤素等对环境不友好的化学改性元素来实现有效阻燃。但是，如何通过超低添加量的阻燃剂来制备一种具备优异阻燃性能且力学性能优异的硅橡胶泡沫材料仍是一个重要的挑战。
发明内容
针对本领域存在的不足之处，本发明提供了一种阻燃发泡剂，添加极少量的二维纳米材料即可实现阻燃性能。利用物理共混的方法将发泡助剂与硅油混合，发泡助剂包裹二维纳米材料可更好的实现二维纳米材料在硅油中的分散；用所述阻燃发泡助剂制备得到的硅橡胶泡沫材料中，二维纳米材料的表面羟基与含氢硅油反应，利用此反应，超低含量的二维纳米材料片层在发泡过程中会原位组装到硅橡胶泡孔表面，形成致密的保护层，能够有效阻止火焰对材料内部的有机分子热分解，实现超低含量的高效、绿色阻燃效果。
一种阻燃发泡剂，按原料总质量为100％计，原料组成包括：
作为优选，所述的阻燃发泡剂，按原料总质量为100％计，原料组成包括：
作为优选，所述的二维纳米材料选自功能化石墨烯、氧化石墨烯、石墨烯纳米带、层状纳米硅酸盐片层、片层状纳米氢氧化铝、片层状纳米氢氧化镁、纳米过渡金属硫化物(如二硫化钼)等中的至少一种，此类二维纳米材料的片层可更有效的组装在泡孔表面以起到阻止火焰进一步进攻材料的作用，达到更优异的阻燃效果。
作为优选，所述的多元醇选自乙二醇、季戊四醇、1,2-丙二醇、新戊二醇、二缩二乙二醇、一缩二丙二醇、三羟甲基丙烷、1,4-丁二醇、丙三醇中的至少一种。这些优选的多元醇可更有效地与二维纳米材料反应，有助于二维纳米材料在发泡助剂中的稳定性。
作为优选，所述的增溶助剂选自L580硅酮表面活性剂、三甲基硅醇、道康宁5562醇醚硅油中的至少一种。这些增溶助剂可更好的降低所制备的发泡助剂的表面张力，提高二维纳米材料在发泡助剂中的的稳定性。
作为优选，所述羟基硅胶的粘度为1000～50000mPa·s，侧链含甲基和/或苯基，优选区间硅胶的分子量所制备的材料的加工与力学性能更加优异。
本发明还提供了一种所述的阻燃发泡剂的制备方法，将二维纳米材料和多元醇混合均匀后在80～120℃反应2～4h，然后加入增溶助剂和羟基硅胶混合均匀得到所述的阻燃发泡剂。
本发明还提供了一种阻燃硅橡胶泡沫材料，使用所述的阻燃发泡剂作为发泡助剂，按原料总质量为100％计，原料组成包括：
作为优选，所述含氢硅油的粘度为20～50mPa·s，活性氢质量分数为0.2％～1.6％。
作为优选，所述羟基硅胶的粘度为1000～50000mPa·s，侧链含甲基和/或苯基。
作为优选，所述的抑制剂选自马来酸二烯丙酯、3-甲基-1-炔-3-醇、乙炔基环己醇、富马酸二乙酯等中的至少一种。
作为优选，所述乙烯基硅油的粘度为1000～55000mPa·s，乙烯基含量为0.15wt％～0.36wt％。
作为优选，所述的催化剂为铂催化剂，如卡斯特铂催化剂。进一步优选，所述催化剂的铂含量为500～6000ppm。
作为优选，所述的阻燃硅橡胶泡沫材料，按原料总质量为100％计，原料组成包括：
本发明还提供了一种所述的阻燃硅橡胶泡沫材料的制备方法，包括步骤：
(1)将含氢硅油、羟基硅胶、发泡助剂和抑制剂混合均匀得到组分A；
按组分A总质量为100％计，各组分加入量为：
(2)将羟基硅胶、乙烯基硅油、催化剂混合均匀得到组分B；
按组分B总质量为100％计，各组分加入量为：
(3)将组分A和组分B等质量混合均匀，于20～100℃下交联固化后，于110～130℃下后硫化制得所述的阻燃硅橡胶泡沫材料。
作为优选，所述交联固化时间为1～30min。
作为优选，所述后硫化时间为0.5～2h。
本发明利用物理分散实现阻燃发泡剂在基体中的良好分散，调控二维纳米材料在发泡助剂中的稳定性，避免其迁移到有机硅基体内部。此外，与传统物理共混和表面涂敷技术相比，本发明利用二维纳米材料表面羟基与硅油反应，在泡孔表面原位反应组装超薄二维纳米材料保护层，实现超低含量的高效、绿色阻燃效果，制备出轻质、阻燃、高弹的阻燃硅橡胶泡沫纳米复合材料。
本发明绿色环保，制备工艺简单，所制材料泡孔均匀，阻燃效果优异，在不影响力学性能的条件下可达到UL-94 V0级，这使得该方法制得的阻燃硅橡胶泡沫材料在航空航天、轨道交通、汽车、电子电器等领域有良好的应用前景。
本发明与现有技术相比，主要优点包括：
(1)本发明开发了一种制备阻燃材料的新方法，通过将二维纳米填料制作成发泡助剂，实现了超低含量的填料就可有实现阻燃的性能。
(2)制备工艺简单，方法绿色。
(3)超低含量的二维纳米材料片层在发泡过程中会原位组装到硅橡胶泡孔表面，形成致密的保护层，能够有效阻止火焰对材料内部的有机分子热分解，进而实现材料高效的绿色阻燃效果，该阻燃型硅橡胶泡沫材料的阻燃等级达UL-94 V0级，同时其力学性能优异且具有良好的疏水性能。
附图说明
图1为实施例1的阻燃硅橡胶泡沫材料的扫描电镜照片；
图2为对比例1的纯硅橡胶泡沫材料的扫描电镜照片；
图3为实施例1的阻燃硅橡胶泡沫材料(B)和对比例1的纯硅橡胶泡沫材料(A)的燃烧测试图。
具体实施方式
下面结合附图及具体实施例，进一步阐述本发明。应理解，这些实施例仅用于说明本发明而不用于限制本发明的范围。下列实施例中未注明具体条件的操作方法，通常按照常规条件，或按照制造厂商所建议的条件。
实施例1
取0.2g直径为15μm的氧化石墨烯片和20g乙二醇，混合均匀后置于100℃条件下2小时，后加入0.2g三甲基硅醇和20g粘度为5000mPa·s的羟基硅胶，机械搅拌充分混合均匀后制得具有阻燃功能的发泡助剂。
取含氢量0.5％、粘度20mPa·s的含氢硅油25g、粘度1 Pa·s的羟基硅胶55g、3.2g发泡助剂和0.01g的马来酸二烯丙酯，机械搅拌均匀制得A组分；同时，取1 Pa·s羟基硅胶40g，乙烯基含量0.3％、粘度1 Pa·s的乙烯基硅油40g和2000ppm的卡斯特铂催化剂0.4g，机械混合均匀制得B组分。
分别取20g A组分与20g B组分，机械搅拌充分混和均匀，放于80℃烘箱中放置10分钟使其交联固化，后放置于120℃鼓风烘箱中1小时后硫化，制得阻燃硅橡胶泡沫材料。扫描电镜图结果如图1所示，添加了阻燃发泡剂的硅橡胶泡沫材料因为泡孔内原位组装了石墨烯片二维纳米填料，泡孔内表面粗糙。
对比例1
与实施例1相比，区别仅在于发泡助剂中无二维纳米材料，其他条件均相同，制得纯硅橡胶泡沫材料。扫描电镜图结果如图2所示，未添加氧化石墨烯片的硅橡胶泡沫的泡孔内表面光滑。
将实施例1所制备的阻燃硅橡胶泡沫材料(记为B)和对比例1制备的纯硅橡胶泡沫材料(记为A)剪成固定的样条做垂直燃烧测试，如图3所示，结果表明，添加了氧化石墨烯片的阻燃硅橡胶泡沫材料(B)具有优异的阻燃效果，达到UL-94 V0级阻燃等级。
实施例2
取0.15g直径为20μm的石墨烯纳米带和20g新戊二醇，混合均匀后置于100℃条件下2小时，后加入0.2g L580硅酮表面活性剂和20g粘度为1Pa·s的羟基硅胶，机械搅拌充分混合均匀后制得发泡助剂。
取含氢量0.5％、粘度50mPa·s的含氢硅油30g、粘度2Pa·s的羟基硅胶50g、4.5g发泡助剂和0.05g的3-甲基-1-炔-3-醇，机械搅拌均匀制得A组分；同时，取1Pa·s羟基硅胶40g，乙烯基含量0.3％、粘度1Pa·s的乙烯基硅油40g和5000ppm的卡斯特铂催化剂0.4g，机械混合均匀制得B组分。
分别取20g A组分与20g B组分，机械搅拌充分混和均匀后放于80℃烘箱中放置10分钟使其交联固化，后放置于120℃鼓风烘箱中1小时后硫化，制得阻燃硅橡胶泡沫材料。
实施例3
取0.3g直径为30μm的片层状纳米氢氧化铝和二缩二乙二醇15g，混合均匀后置于100℃条件下2小时，后加入0.3g道康宁5562醇醚硅油和20g粘度为2Pa·s的羟基硅胶，机械搅拌充分混合均匀后制得发泡助剂。
取含氢量0.5％、粘度200mPa·s的含氢硅油30g、粘度2Pa·s的羟基硅胶50g、3.0g发泡助剂和0.2g的乙炔基环己醇，机械搅拌均匀制得A组分；同时，取1Pa·s羟基硅胶30g，乙烯基含量0.4％、粘度1Pa·s的乙烯基硅油50g和2000ppm的卡斯特铂催化剂0.6g，机械混合均匀制得B组分。
分别取20g A组分与20g B组分，机械搅拌充分混和均匀后放于80℃烘箱中放置10分钟使其交联固化，后放置于120℃鼓风烘箱中1小时后硫化，制得阻燃硅橡胶泡沫材料。
实施例4
取0.25g直径为50μm的二硫化钼和三羟甲基丙烷10g，混合均匀后置于100℃条件下2小时，后加入0.2g L580硅酮表面活性剂和20g粘度为8000mPa·s的羟基硅胶，机械搅拌充分混合均匀后制得发泡助剂。
取含氢量1.6％、粘度20mPa·s的含氢硅油30g、粘度2Pa·s的羟基硅胶50g、2g发泡助剂和0.1g的聚山梨酯-80，机械搅拌均匀制得A组分；同时，取5000mPa·s羟基硅胶30g，乙烯基含量0.25％、粘度5000mPa·s的乙烯基硅油50g和4500ppm的卡斯特铂催化剂0.6g，机械混合均匀制得B组分。
分别取20g A组分与20g B组分，机械搅拌充分混和均匀后放于80℃烘箱中放置10分钟使其交联固化，后放置于120℃鼓风烘箱中1小时后硫化，制得阻燃硅橡胶泡沫材料。
实施例5
取0.5g直径为25μm的功能化石墨烯和1,4-丁二醇30g，混合均匀后置于100℃条件下2小时，后加入0.4g三甲基硅醇和20g粘度为6000mPa·s的羟基硅胶，机械搅拌充分混合均匀后制得发泡助剂。
取含氢量0.2％、粘度50mPa·s的含氢硅油15g、粘度5Pa·s的羟基硅胶50g、5g发泡助剂和1.0g的失水山梨糖醇脂肪酸酯，机械搅拌均匀制得A组分；同时，取5000mPa·s羟基硅胶20g，乙烯基含量0.40％、粘度1Pa·s的乙烯基硅油60g和3000ppm的卡斯特铂催化剂1.2g，机械混合均匀制得B组分。
分别取20g A组分与20g B组分，机械搅拌充分混和均匀后放于80℃烘箱中放置10分钟使其交联固化，后放置于120℃鼓风烘箱中1小时后硫化，制得阻燃硅橡胶泡沫材料。
此外应理解，在阅读了本发明的上述描述内容之后，本领域技术人员可以对本发明作各种改动或修改，这些等价形式同样落于本申请所附权利要求书所限定的范围。
Claims (10)
1.一种阻燃发泡剂，其特征在于，按原料总质量为100％计，原料组成包括：
2.根据权利要求1所述的阻燃发泡剂，其特征在于，按原料总质量为100％计，原料组成包括：
3.根据权利要求1或2所述的阻燃发泡剂，其特征在于，所述的二维纳米材料选自功能化石墨烯、氧化石墨烯、石墨烯纳米带、层状纳米硅酸盐片层、片层状纳米氢氧化铝、片层状纳米氢氧化镁、纳米过渡金属硫化物中的至少一种。
4.根据权利要求1或2所述的阻燃发泡剂，其特征在于，所述羟基硅胶的粘度为1000～50000mPa·s，侧链含甲基和/或苯基。
5.一种根据权利要求1～4任一权利要求所述的阻燃发泡剂的制备方法，其特征在于，将二维纳米材料和多元醇混合均匀后在80～120℃反应2～4h，然后加入增溶助剂和羟基硅胶混合均匀得到所述的阻燃发泡剂。
6.一种阻燃硅橡胶泡沫材料，其特征在于，使用权利要求1～4任一权利要求所述的阻燃发泡剂作为发泡助剂，按原料总质量为100％计，原料组成包括：
7.根据权利要求6所述的阻燃硅橡胶泡沫材料，其特征在于，按原料总质量为100％计，原料组成包括：
8.根据权利要求6或7所述的阻燃硅橡胶泡沫材料，其特征在于，所述含氢硅油的粘度为20～50mPa·s，活性氢质量分数为0.2％～1.6％。
9.根据权利要求6或7所述的阻燃硅橡胶泡沫材料，其特征在于，所述乙烯基硅油的粘度为1000～55000mPa·s，乙烯基含量为0.15wt％～0.36wt％。
10.一种根据权利要求6～9任一权利要求所述的阻燃硅橡胶泡沫材料的制备方法，包括步骤：
(1)将含氢硅油、羟基硅胶、发泡助剂和抑制剂混合均匀得到组分A；
按组分A总质量为100％计，各组分加入量为：
(2)将羟基硅胶、乙烯基硅油、催化剂混合均匀得到组分B；
按组分B总质量为100％计，各组分加入量为：
羟基硅胶 20％～50％，
乙烯基硅油 10％～80％，
催化剂 0.2％～6％；
(3)将组分A和组分B等质量混合均匀，于20～100℃下交联固化后，于110～130℃下后硫化制得所述的阻燃硅橡胶泡沫材料。
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